Porous liquid absorbing-and-holding member, process for production thereof, and alcohol absorbing-and-holding member

ABSTRACT

An object of the present invention is to provide a porous liquid absorbing-and-holding member having a high absorbing capacity for a liquid owing to capillarity and having in itself a structure capable of holding a large amount of the liquid, a process for producing this member, and a member for absorbing and holding an alcohol used as a fuel for a fuel cell. The porous liquid absorbing-and-holding member provided by the present invention is that including a porous sintered product having a skeleton formed by sintering of metal powder around voids and subjected to hydrophilicity-imparting treatment. The hydrophilicity-imparting treatment is preferably the formation of one or more substances selected from the group consisting of silicon oxides, titanium oxides, chromium oxides and aluminum oxide on the skeleton.

BACKGROUND OF THE INVENTION

The present invention relates to a porous liquid absorbing-and-holdingmember having absorbing capacity for a liquid such as an alcohol orwater and capable of holding the liquid, a process for productionthereof, and an alcohol absorbing-and-holding member.

When brought into contact with a liquid, porous materials (e.g. spongeand a fibrous substrate) made of a resin or a natural material canabsorb the liquid to hold the same therein, owing to capillarity due tosurface tension. The sponge, fibrous substrate and the like, however,have a low strength in themselves and hence cannot retain their shape.Therefore, porous ceramics represented by unglazed pottery are usuallyused as porous materials having high strength and water retentioncapacity.

In the field of fuel cells that have recently been noted, it has beenproposed that a porous material be used as a member for feeding anaqueous methanol solution to the fuel electrode (anode) of a directmethanol fuel cell (hereinafter abbreviated as DMFC) (JP-A-59-066066).That is, the porous material is suitable because it can absorb theaqueous methanol solution from a tank owing to capillarity to holdmethanol on the surface of the fuel electrode.

As described above, porous materials are useful as a liquidabsorbing-and-holding member. Conventional porous materials aredisadvantageous in that they can hold a liquid therein in only a smallamount for their volume. For example, in the case of DMFC, since aporous material has to feed a fuel to the anode ceaselessly, the porousmaterial has to send the liquid fuel to the anode owing to capillarityand moreover, the porous material itself has to be able to hold the fuelas much as possible. Therefore, the conventional porous materials arenot satisfactory. When used in a mobile or an automobile, a porousmaterial has to be resistant to a certain degree of vibration andimpact. Therefore, conventional ceramics are not satisfactory inquality.

An object of the present invention is to provide a porous liquidabsorbing-and-holding member having a high absorbing capacity for aliquid owing to capillarity and having in itself a structure capable ofholding a large amount of the liquid, a process for producing thismember, and a member for absorbing and holding an alcohol used as a fuelfor a fuel cell.

SUMMARY OF THE INVENTION

The present inventor investigated porous materials and consequentlysolved the above problem by producing a metallic porous sintered producthaving not a simple sintered structure but a skeleton formed bysintering of metal particles around voids, and subjecting the metalsurface of the skeleton to hydrophilicity-imparting treatment. On thebasis of this technical idea that a highly hydrophilic substance isformed on the surface of skeleton of the porous sintered productcomprising the metallic structure, the present inventor has foundoptimum method and conditions for forming said hydrophilic substance,and has accomplished the present invention.

That is, the present invention provides a porous liquidabsorbing-and-holding member characterized by comprising a poroussintered product having a skeleton formed by sintering of metal powderaround voids and subjected to hydrophilicity-imparting treatment. Thehydrophilicity-imparting treatment is preferably the formation of one ormore substances selected from the group consisting of silicon oxides,titanium oxides, chromium oxides and aluminum oxide on the skeleton.

In addition, in the porous liquid absorbing-and-holding member of thepresent invention, the skeleton portion has pores with an average poresize of preferably 200 μm or less, the average void size is preferably3,000 μm or less, and the porosity content of the whole porous materialis preferably not more than 95% by volume and not less than 60% byvolume. More preferably, the average pore size of the skeleton portionis 5 to 100 μm, the average void size is 100 to 2,000 μm, and theporosity content of the whole porous material is 70 to 90% by volume.The present invention also provides an alcohol absorbing-and-holdingmember comprising the above-mentioned porous liquidabsorbing-and-holding member into which an alcohol is absorbed to beheld therein. In the present specification, “average pore (void) size”denotes average of pore (void) diameter.

Furthermore, the present invention provides a process for producing aporous liquid absorbing-and-holding member by adopting a method forsubjecting the skeleton of a porous sintered product having the skeletonformed by sintering of metal powder around voids tohydrophilicity-imparting treatment, which is characterized by carryingout the hydrophilicity-imparting treatment by using an organometalliccompound as a starting material, and reacting a starting gas obtained byvaporizing this compound with a plasma gas containing oxygen at apressure close to atmospheric pressure, to form a metal oxide on thesurface of the above-mentioned skeleton.

The present invention provides the above-mentioned process for producinga porous liquid absorbing-and-holding member in which the plasma gascontaining oxygen at a pressure close to atmospheric pressure ispreferably passed upward from below the porous sintered product to formthe metal oxide on the surface of the skeleton. In addition, the presentinvention provides the above-mentioned process for producing a porousliquid absorbing-and-holding member which is characterized in that themetal oxide is a silicon oxide.

The present invention has made it possible to provide a porous liquidabsorbing-and-holding member having a high absorbing capacity for aliquid owing to capillarity and having a structure capable of holding alarge amount of the liquid, a process for producing this member, and amember for absorbing and holding an alcohol used as a fuel for a fuelcell.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an electron micrograph showing an example of section of aporous liquid absorbing-and-holding member beforehydrophilicity-imparting treatment according to the present invention.

FIG. 2 is an electron micrograph showing an example of the skeletonportion of a porous liquid absorbing-and-holding member of the presentinvention.

FIG. 3 is an electron micrograph showing an example of section of theskeleton of the porous liquid absorbing-and-holding member of thepresent invention.

FIG. 4 is an electron micrograph showing another example of section ofthe skeleton of the porous liquid absorbing-and-holding member of thepresent invention.

FIG. 5 is an electron micrograph showing an example of the skeletonportion of another porous liquid absorbing-and-holding member of thepresent invention.

FIG. 6 is a graph showing an example of the result of analyzing theskeleton portion of the porous liquid absorbing-and-holding member ofthe present invention.

FIG. 7 is an electron micrograph showing an example of the skeletonportion of further another porous liquid absorbing-and-holding member ofthe present invention.

FIG. 8 is an electron micrograph showing an example of section ofanother porous liquid absorbing-and-holding member beforehydrophilicity-imparting treatment according to the present invention.

FIG. 9 is an electron micrograph showing an example of the skeletonportion of still another porous liquid absorbing-and-holding member ofthe present invention.

FIG. 10 is an electron micrograph showing another example of theskeleton portion of the porous liquid absorbing-and-holding member ofthe present invention.

FIG. 11 is an electron micrograph showing an example of the skeletonportion of a porous liquid absorbing-and-holding member of a comparativeexample.

FIG. 12 is an electron micrograph showing an example of the skeletonportion of a porous liquid absorbing-and-holding member of anothercomparative example.

FIG. 13 is a diagram illustrating a test for evaluation of liquidabsorbing-and-holding capability carried out in the working examples.

FIG. 14 is a graph showing the result of evaluating the liquidabsorbing-and-holding capability of porous liquid absorbing-and-holdingmembers of the present invention and a comparative example.

FIG. 15 is a graph showing the result of evaluating the liquidabsorbing-and-holding capability of porous liquid absorbing-and-holdingmembers of the present invention and another comparative example.

FIG. 16 is a schematic view showing an example of CVD apparatus used inthe production process of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

At first, the porous liquid absorbing-and-holding member of the presentinvention is described below. The important characteristic of thismember is that an excellent action of absorbing and holding a liquid isattained by using as a basic structure a sintered porous product havinga skeleton formed by sintering of metal powder around voids, and forminga highly hydrophilic substance on the metal surface of the skeleton, forexample, by coating treatment or self-production such as oxidationtreatment. That is, because of the structure formed by surrounding ofvoids with sintered portions of metal powder, the member is composed ofa skeleton portion capable of sucking up a liquid and void portionscapable of storing the liquid, and the surface of the skeleton has anexcellent wettability owing to the hydrophilicity-imparting treatment.Therefore, the member has a further improved liquidabsorbing-and-holding capability.

A detailed explanation is given below. Because of the formation of theskeleton by sintering of metal powder, a liquid is absorbed at firstowing to capillarity caused by the pores of the skeleton portion. Theabsorbed liquid oozes out into voids present around the skeleton portionto fill the voids therewith, whereby the liquid is held. In thisprocess, since the skeleton of the liquid absorbing-and-holding memberof the present invention has the highly hydrophilic substance formedthereon, the wettability of the surface of the skeleton is excellent,resulting in an improved absorbing-and-holding capability in the aboveprocess. In this case, when the enhancement of the hydrophilicity of thesubstance formed for the hydrophilicity-imparting treatment andoptionally the reduction of the void size described hereinafter arecarried out, the liquid-sucking-up action is improved by the help of thecapillarity of the voids themselves. Depending on purpose of use, spacescan be secured also after the liquid absorption to assure airpermeability, by setting the void size at a rather large size and makingthe voids intercommunicative.

In the present invention, since an absorbing-and-holding member for fuelfor DMFC used in a mobile or an automobile is also supposed, the metalskeleton is used for improving the vibration resistance and the impactresistance and hence the metal powder is used as a starting material. Inaddition, a metallic material is suitable as a material for absorbingand holding a liquid because it generally has a high surface tension initself and hence has a good wettability with the liquid and itswettability can be further improved by employing thehydrophilicity-imparting treatment according to the present invention.As to the kind of the metallic material, it is effective to choose ametallic material hardly affectable by a liquid to be absorbed and heldby the use of the material. It is also possible to impart a function asa current-collecting plate or an electrode to the metallic material atthe same time by utilizing the electroconductivity of the metal.

Although the hydrophilic substance formed on the skeleton in the presentinvention need not be particularly specified, various metal (includingsemi-metals) oxides and organic substances such as celluloses areeffective as the hydrophilic substance. That is, it is conjectured thatthe oxides improve the wettability because oxygen in the oxide ishydrophilic. In addition, it is conjectured that the celluloses areeffective as organic substances excellent in chemical resistance becausethey have an excellent hydrophilicity and are difficultly soluble in aliquid.

In the case of the metal (including semi-metals) oxides, the metalsurface of the skeleton portion is coated with a highly hydrophilicsubstance such as a titanium oxide represented by titania, a chromiumoxide represented by chromia, or a silicon oxide represented by silica.Aluminum oxide (alumina) may also be used. As a coating means, asolution of an alkoxide or the like of a metal to be converted to themetal oxide may also be used besides oxidation treatment, conversiontreatment and chemical vapor deposition (CVD) treatment. In the case ofcoating treatment using the alkoxide, it is important to adjust theviscosity of the alkoxide solution to a low value so that the coatingsubstance may not block up the pores of the skeleton portion.

A preferable structure according to the present invention is explainedbelow.

(1) The pore size of the skeleton portion is preferably 200 μm or lesson average.

This range is for assuring the sufficient liquid-sucking-up capabilitydue to capillarity of the skeleton portion.

(2) The void size is preferably 3,000 μm or less on average.

This is because the absorbing properties and holding properties for aliquid tend to be deteriorated when the void size is too large. It canbe speculated that the deterioration is caused because gravity appliedto a liquid stored in voids surpasses an action of drawing up the storedliquid. It is conjectured that a small void size is advantageous becauseit accelerates capillarity as in the case of the pores of the skeletonportion, permits stable holding of a liquid in the voids, andcontributes also to the absorption.

(3) The porosity content of the whole porous material is preferably notmore than 95% by volume and not less than 60% by volume.

This is because the increase of voids for holding a liquid isadvantageous for increasing the amount of the liquid held in the porousmaterial. In addition, when the voids are isolated from one another bythe skeleton portion, the skeleton portion is previously filled with theliquid because the movement of the liquid is rapid in the skeletonportion owing to capillary force. As a result, when the voids aretightly covered with the skeleton portion, air in the voids hardlyescapes, so that entrapped air is likely to be produced to inhibit theliquid from entering the voids. For preventing this inhibition, it iseffective to improve the inter-communication of the voids to a certaindegree so that when the liquid enters the voids, air in the voids can beeliminated from the porous material as much as possible. For the abovereasons, the porosity content of the whole porous material is preferably60% by volume or more.

However, on the other hand, it is necessary to assure a sufficientvolume percentage of the skeleton portion for assuring the strength ofthe porous material itself and a sufficient liquid-absorbing-capacity.Therefore, the porosity content of the whole porous material ispreferably 95% by volume or less.

The porous liquid absorbing-and-holding member of the present inventionis more preferably as follows: in the sintered product having theskeleton formed thereon, the skeleton is a sintered skeleton of metalpowder having an average particle size of 100 μm or less, the pore sizeof the skeleton portion is 5 to 100 μm on average, the void size is 100to 2,000 μm on average, and the porosity content of the whole porousmaterial is 70 to 90% by volume.

As a process for producing the porous material used in the presentinvention, the following process, for example, can be adopted.

At first, metal powder is prepared. As the metal powder, stainlesssteel, titanium, titanium alloys and the like, but not materials easilycorrodible by a liquid to be brought into contact with them, areeffective. As to the particle size of the metal powder, its averageparticle size is preferably 200 μm or less, more preferably 100 μm orless.

The metal powder is mixed with resin particles and a binder. As theresin particles, resin particles having an average particle size of 100to 3,000 μm are preferable for assuring the void size. Although a resinmay also be used as the binder, it is effective to use, for example, abinder composed mainly of methyl cellulose and water which is insolublein a solvent, when an effective method comprising removal of the resinparticles by the use of the solvent is adopted.

Then, from the kneaded product thus obtained, a molded product isproduced, debound by heating and then sintered. Here, when water isincorporated into the above-mentioned binder, a drying step ispreferably added after the molding. When the resin particles are removedby the use of the solvent, steps of solvent extraction and drying arepreferably added before the debinding by heating.

The porous material obtained by the sintering is preferably subjected tothe following hydrophilicity-imparting treatment, whereby it is possibleto obtain the porous liquid absorbing-and-holding member of the presentinvention in which the skeleton formed by sintering of the metal powderaround voids has a hydrophilic substance formed thereon. This member canbe used as an alcohol absorbing-and-holding member.

The process for producing a porous liquid absorbing-and-holding memberof the present invention is explained below. The importantcharacteristic of the production process of the present invention is toutilize a special chemical vapor deposition method (CVD method) forcarrying out hydrophilicity-imparting treatment for forming a highlyhydrophilic substance on the surface of the skeleton of a poroussintered product used as a substrate for the member. The term“hydrophilicity-imparting treatment” used herein means a treatment forimproving the wettability with, in particular, water or an organiccompound having a hydroxyl group.

First, in the production process of the present invention, thehydrophilic substance formed on the skeleton is a metal oxide. Thereason is as follows. The metal oxide is excellent in adhesiveproperties to the skeleton made of metal and moreover, it is generally achemically stable substance and hence is advantageous in that it permitsprevention of a corrosion problem caused when the porous liquidabsorbing-and-holding member is used in a water-containing liquid as inthe present invention and various problems caused by various reactions.In addition, the wettability is improved because oxygen in the metalsubstance is hydrophilic. The metal oxide referred to herein includessemi-metal oxides.

The production process of the present invention is characterizedparticularly in that a special method, i.e., a plasma CVD method is usedin the process in order to form the above-mentioned metal oxide on theskeleton surface. The plasma CVD method is a method in which a compoundcontaining a starting material is decomposed by the use of plasma tocause a chemical reaction and form a substance film on the surface of aheated substrate (an object to be treated). In the present invention, anorganometallic compound is used as a starting material and a startinggas obtained by vaporizing this compound is reacted with a plasma gascontaining oxygen at a pressure close to atmospheric pressure, to form ametal oxide on the surface of the above-mentioned skeleton.

The reason why the organometallic compound is used as a startingmaterial is that even if the vapor pressure of its metal is low, thecompound can easily be gasified and then fed to a reaction chamber. Inaddition, a thin film having any of various compositions can be grown bychanging the gas. As to the decomposition of the starting gas obtainedby the vaporization, by the use of plasma gas, the starting gas can bedecomposed at a lower temperature as compared with a conventionalthermal CVD method. Therefore, the thermal deformation of the substrateitself and peeling of the metal oxide from the substrate by thedifference between them in thermal expansion can be suppressed. Thefilmy oxide formed by the plasma CVD method is dense and is good inthrowing power even on the inner surface of the substrate even when theshape of the substrate is complicated like that of the porous materialused in the present invention. Therefore, the filmy oxide is mostsuitable particularly for the surface treatment of the complicatedskeleton of the metallic porous material which is intended in thepresent invention.

For introducing oxygen necessary for producing the metal oxide used inthe present invention, a large-scale apparatus such as a high-vacuumchamber like that used in a vacuum plasma CVD method is not necessarybecause a plasma gas containing oxygen at a pressure close toatmospheric pressure can be used. That is, film-forming treatmentsubstantially in the air is possible and the treatment can becontinuously carried out. Therefore, the apparatus cost can be greatlyreduced and the productivity is high. The term “a pressure close toatmospheric pressure” means a pressure in the range of about 13 to 200kPa, preferably a pressure of about 100 kPa. A pressure in the aboverange is considered herein as atmospheric pressure.

The present inventor ascertained that in using the above-mentionedplasma gas, the following is very effective for stable formation of themetal oxide: preferably, the plasma gas is passed upward from below aporous material to be treated, to form the metal oxide by reaction onthe surface of skeleton of the porous material (FIG. 16). The reason forthis effectiveness is as follows: since the plasma gas used for formingthe oxide is in a heated state at about 400° C. and flows upward owingto a rising current of air, passing the plasma gas upward gives thedirection of the smoothest flow not contrary to the flow of the gas.

As a method for forming the metal oxide on the skeleton of the porousmaterial, there is also another method using a solution of an alkoxideor the like of a metal to be converted to the metal oxide. When coatingtreatment using the alkoxide is carried out particularly on the sinteredskeleton, it is important to adjust the viscosity of the alkoxidesolution to a low viscosity so that the coating material may not blockup the pores of the skeleton portion. Therefore, strict control isnecessary. On the other hand, the CVD method adopted in the presentinvention is advantageous in that the metal oxide can be formed whilesecuring the pores certainly.

As the metal oxide formed so as to cover the metal skeleton in thepresent invention, silicon oxides, titanium oxides, chromium oxides andaluminum oxides can be selected as highly hydrophilic substances. Ofthese, the silicon oxides are preferably selected which are mostcommonly used in the field of semiconductors, because this selection isadvantageous from the viewpoint of starting material and cost.

DESCRIPTION OF PREFERRED EMBODIMENT EXAMPLE 1

SUS316L powder obtained by water atomization and having an averageparticle size of 60 μm, commercial methyl cellulose and two kinds ofspherical paraffin wax particles with average particle sizes of 1,000 μmand 180 μm, respectively, as rein particles were mixed and then kneadedwith water and a plasticizer to prepare a kneaded product. The amount ofthe resin particles mixed was set as follows: when the total volume ofthe metal powder and the resin particles was taken as 100%, theproportions of the paraffin wax particles with an average particle sizeof 1,000 μm and the paraffin wax particles with an average particle sizeof 180 μm were 75% and 12.5%, respectively, and the balance 12.5% was ofthe metal powder.

The above-mentioned kneaded product was press-molded into a plate undera load of 0.8 MPa, and this molded product was dried at 50° C. Theparaffin wax particles in the molded product were extracted with asolvent and the molded product thus treated was dried at 70° C.Subsequently, the molded product was heated at a rate of 40° C./h in anitrogen atmosphere in a debinding furnace and maintained at 600° C. for2 hours. By this procedure, the residual paraffin wax and the binderwere decomposed and vaporized. Then, the molded product was sintered byits maintenance at 1,170° C. for 2 hours in hydrogen in a sinteringfurnace, to obtain a disk of porous material having a thickness of 3 mm.

The microscopic shape of section of the porous sintered product obtainedis shown in the scanning electron microscope (SEM) photograph in FIG. 1.The blank portions show metal portions and the dark portions show voidsand spaces constituting the pores of the skeleton portion. The pore sizeof the skeleton portion was measured by a mercury injection method andfound to be 79.4 μm on average. As the voids, there are confirmed twokinds of voids, i.e., small voids that look dispersed in the skeletonand large voids that do not look dispersed in the skeleton. On the basisof the section micrograph, it was found that the diameter of the smallvoids was 150 μm on average, the diameter of the large voids 660 μm onaverage, the diameter of whole voids 510 μm on average, and the porositycontent of the whole porous material 84.8%.

A stock (105 mm long, 20 mm wide and 3 mm thick) was cut out of theporous sintered product and set in a plasma gas producing apparatus forforming a metal oxide on the surface of the internal skeleton. Thesetting was conducted as follow: as shown in FIG. 16, a schematic viewof the apparatus, the surface on which the oxide was to be formed wasplaced downward, so that a plasma gas might be brought into contact withthis surface from below the surface. TEOS (tetraethoxysilane) was usedas a starting organometallic compound. While feeding this startingmaterial at a rate of 0.2 g/min to the surface of the substrate from theside by using nitrogen gas as a carrier gas, a 1:1 (by volume) mixed gasof oxygen and nitrogen converted to plasma at atmospheric pressure waspassed upward toward the surface to be treated of the substrate, to bereacted with the starting gas, whereby a precursor of film was formed.The precursor accumulated on the surface of the porous sintered productto form a silicon oxide film. By the above atmospheric plasma CVDtreatment, the surface of the skeleton portion was coated with silicafor 5 minutes to produce a test piece.

FIG. 2 is a SEM photograph showing the metal surface of the skeletonafter the CVD treatment. It can be seen from FIG. 2 that the pores arenot blocked up by the coating material. The SEM photograph in FIG. 3shows a section of the skeleton surface in the vicinity of the treatedsurface of the test piece. As shown in FIG. 3, a silicon oxide (SiO₂)film of about 60 nm in thickness was formed. The SEM photograph in FIG.4 shows a section of the skeleton surface at a distance of 1.5 mm fromthe treated surface of the test piece. As shown in FIG. 4, a siliconoxide film of about 30 nm in thickness was formed. As a result ofanalysis with an energy dispersion X-ray analyzer (EDX), the silicon andoxygen contents of the metal surface layer of the skeleton portion werefound to be higher than before the CVD treatment, and it was found thateven the skeleton surface inside the test piece had been thinly anduniformly coated with silicon oxide.

EXAMPLE 2

A porous sintered product (105 mm long, 20 mm wide and 3 mm thick)obtained in the same manner as in Example 1 was washed, coated with aperoxotitanic acid solution and then heat-treated at 400° C. in the airto produce a test piece. FIG. 5 is a SEM photograph showing the metalsurface of the skeleton portion. Scaly precipitate portions are observedon the surface and it can be seen that the pores are not blocked up.FIG. 6 shows the result of EDX analysis of the precipitate portions. Theprecipitate portions were found to have high titanium and oxygencontents and it was confirmed that titanium oxide had been precipitatedon the metal surface though nonuniformly.

EXAMPLE 3

A porous sintered product (105 mm long, 20 mm wide and 3 mm thick)obtained in the same manner as in Example 1 was washed and thensubjected to passive-state treatment with 60% concentrated nitric acidto form a chromium oxide coating film on the metal surface of theskeleton. FIG. 7 is a SEM photograph of the metal surface of theskeleton portion. It can be seen from FIG. 7 that the pores are notblocked up. As to the chromium oxide, the chromium and oxygen contentsof the metal surface layer of the skeleton portion were found to behigher than before the treatment as a result of EDX analysis, and it wasconfirmed that the skeleton surface had been thinly and uniformly coatedwith the chromium oxide.

EXAMPLE 4

A kneaded product was prepared in the same manner as in Example 1 exceptfor using Fe-3 (mass %) Cr-5 (mass %) Al-0.5 (mass %) Zr powder obtainedby gas atomization and having an average particle size of 52 μm, inplace of the SUS316L powder obtained by water atomization. The amount ofthe resin particles mixed was set so that the proportions of theparaffin wax particles with an average particle size of 1,000 μm and theparaffin wax particles with an average particle size of 180 μm might be80% and 10%, respectively, and that the balance 10% might be of themetal powder. A disc of porous material having a thickness of 5.5 mm wasobtained from the kneaded product in the same manner as in Example 1.

The microscopic shape of section of the porous sintered product obtainedis shown in the SEM photograph in FIG. 8. Although the microscopic shapewas the same as in FIG. 1, the pore size of the skeleton portion was83.1 μm. As to two kinds of confirmed voids, i.e., large voids and smallvoids, it was found on the basis of the section micrograph that thediameter of the small voids was 120 μm on average, the diameter of thelarge voids 560 μm on average, and the average diameter of all the voids290 μm. The porosity content of the whole porous material was 83.7%.

A stock (80 mm long, 20 mm wide and 5.5 mm thick) was cut out of theporous sintered product and coated by precipitating aluminum oxide onthe surface of the skeleton portion by high-temperature oxidationtreatment at 1,100° C. for 1 hour in the air, to produce a test piece.FIG. 9 is a SEM photograph of the skeleton portion after thehigh-temperature oxidation treatment. It can be seen from FIG. 9 thatthe pores are not blocked up by the coating material. FIG. 10 is a SEMphotograph showing the metal surface of the skeleton portion. As aresult of EDX analysis, the aluminum and oxygen contents of the metalsurface layer of the skeleton portion were found to be higher thanbefore the oxidation treatment and it was found that the skeletonsurface had been coated with aluminum oxide.

COMPARATIVE EXAMPLES 1 AND 2

A porous sintered product (105 mm long, 20 mm wide and 3 mm thick)obtained in the same manner as in Example 1 and a porous sinteredproduct (80 mm long, 20 mm wide and 5.5 mm thick) obtained in the samemanner as in Example 4 were used as they were withouthydrophilicity-imparting treatment. The former was used as a test pieceof Comparative Example 1 and the latter as a test piece of ComparativeExample 2. FIG. 11 is a SEM photograph showing the metal surface ofskeleton portion of the test piece of Comparative Example 1, and FIG. 12is a SEM photograph showing the metal surface of skeleton portion of thetest piece of Comparative Example 2.

(Evaluation)

Each of the above-mentioned test pieces, i.e., the test pieces ofExamples 1 to 4 obtained according to the present invention and the testpieces of Comparative Examples 1 and 2 was suspended in a case from anelectronic balance as shown in FIG. 13, 10 mm of the lower end of eachtest piece was immersed in a liquid for test, and the change of theamount of the liquid sucked up per unit sectional area of the test piecewith the immersion time was measured. As the liquid for test, an aqueousmethanol solution having a methanol concentration of 10 mass % was usedas an imaginary methanol solution used in DMFC.

At first, comparison of the test pieces of Examples 1 to 3 andComparative 1 is described below with respect to their sucking-upcapability for the liquid. Since the result of the evaluation testdescribed above is likely to change markedly depending on the conditionof surface of even one and the same test piece, care was taken to allowthe surface of each test piece before the test to assume the samecondition by subjecting the test piece to ultrasonic cleaning withethanol for 2 minutes, followed by drying at 50° C. for 5 hours, beforethe test. In the case of the test piece of Comparative Example 1, notonly the test piece cleaned and then dried under the above conditionsbut also that cleaned for 10 minutes and then dried at 50° C. for 5hours were evaluated.

The graph in FIG. 14 shows the change of the amount of the liquid suckedup per sectional area of each of the test pieces of Examples 1 to 3 andComparative Example 1 with the immersion time. It can be seen from thegraph that the test pieces of Examples 1 to 3 obtained by coating theskeleton of a porous sintered product with each oxide byhydrophilicity-imparting treatment have a higher absorbing capabilitythan does the test piece of Comparative Example 1 not subjected tohydrophilicity-imparting treatment after sintering and subjected tocleaning and drying under the same conditions as above, and that thevalues of the sucking-up amount after 20 minutes (1,200 seconds) of thetest pieces of Examples 1 to 3 are about 4.6 times, about 4.1 times and3.5 times, respectively, that of the test piece of Comparative Example1.

In the case of Comparative Example 1, the test piece cleaned withethanol for 10 minutes before the test was substantially equal insucking-up amount to the test piece of Example 3 obtained by coatingwith chromium oxide according to the present invention, namely, it hadan improved absorbing-and-holding capability. However, when after thetest, this test piece of Comparative Example 1 was dried, allowed tostand for 1 week and then subjected to the same test as above once moreas it was, it was confirmed that this test piece had a deterioratedabsorbing-and-holding capability substantially equal to the result inFIG. 14 obtained for the test piece of Comparative Example 1 cleanedwith ethanol for 2 minutes. That is, the effect of the cleaning for 10minutes does not last. On the other hand, the test pieces of Examples 1to 3 obtained by the hydrophilicity-imparting treatment according to thepresent invention had an unchanged sucking-up amount in a retest evenwhen allowed to stand for 1 week similarly. Thus, it was confirmed thattheir sucking-up capability is hardly changed with the lapse of time andthat their excellent absorbing-and-holding capability lasts.

Next, comparison between the test pieces of Example 4 and Comparative 2is described below with respect to their sucking-up capability for theliquid. In this case, as to cleaning conditions before theabove-mentioned test, care was taken to allow the surface of each testpiece before the test to assume the same condition by subjecting thetest piece to ultrasonic cleaning with ethanol for 10 minutes, followedby drying at 50° C. for 5 hours.

The graph in FIG. 15 shows the change of the amount of the liquid suckedup per sectional area of each of the test pieces of Example 4 andComparative Example 2 with the immersion time. It can be seen from thegraph that the test piece of Example 4 obtained by coating the skeletonof a porous sintered product with aluminum oxide by high-temperatureoxidation treatment (hydrophilicity-imparting treatment) has a higherabsorbing capability than does the test piece of Comparative Example 2not subjected to hydrophilicity-imparting treatment and subjected tocleaning and drying under the same conditions as above, and that thesucking-up amount 10 seconds after the immersion of the test piece ofExample 4 is about 1.4 times that of the test piece of ComparativeExample 2. This improvement ratio corresponds to the ratio of thesucking-up amount of the test piece of Example 1 to that of the testpiece of Comparative Example 1 cleaned for 10 minutes.

It is conjectured that the reason why the time required for thesucking-up amount to reach saturation was short and there was no markeddifference in sucking-up amount at the time of saturation, as comparedwith the result of the test using the test pieces of Examples 1 to 3 andComparative Example 1, is that the length of the test pieces is as shortas 80 mm.

Since the porous liquid absorbing-and-holding member of the presentinvention has a high absorbing capacity for a liquid owing tocapillarity and its porous material itself has a structure capable ofholding a large amount of the liquid, it can be expected to be usablenot only as an absorbing-and-holding member for an alcohol used as afuel for fuel cell but also as a member for absorbing water produced onan air electrode side or a substrate for the electrode of a secondarycell or a capacitor, and the porous liquid absorbing-and-holding membercan be expected to be usable also for producing them.

1-4. (canceled)
 5. A process for producing a porous liquidabsorbing-and-holding member which comprises a porous sintered producthaving a skeleton formed by sintering of metal powder around voids andsubjected to hydrophilicity-imparting treatment, wherein the wholeporous sintered product has a porosity content of not more than 95% byvolume and not less than 60% by volume, and the hydrophilicity-impartingtreatment is the coating of one or more substances selected from thegroup consisting of silicon oxides and titanium oxides on the surface ofthe skeleton, the process comprising: preparing a molded product mixedwith the metal powder, a binder and particles which have been added forassuring void size, which particles are soluble in a solvent, removingsaid particles from said molded product by the use of the solvent,sintering said product after removal of said particles, and subjectingsaid sintered product to the hydrophilicity-imparting treatment forcoating said substances. 6-10. (canceled)
 11. A process according toclaim 5, wherein the hydrophilicity-imparting treatment is the coatingof the silicon oxides.
 12. A process according to claim 5, wherein theskeleton has pores with an average pore size of 5 to 100 μm, the averagevoid size is 100 to 2,000 μm, and the porosity content of the wholeporous material is not more than 90% by volume and not less than 70% byvolume.
 13. A process for producing a porous liquidabsorbing-and-holding member comprising a porous sintered product havinga skeleton formed by sintering of metal powder around voids andsubjected to hydrophilicity-imparting treatment, wherein the wholeporous sintered product has a porosity content of not more than 95% byvolume and not less than 60% by volume, and the hydrophilicity-impartingtreatment is the coating of one or more substances selected from thegroup consisting of silicon oxides and titanium oxides on the skeleton,the process comprising: preparing a molded product mixed with the metalpowder, a binder and resin particles which have been added for assuringvoid size, removing said resin particles from said molded product,sintering said product after removal of said resin particles, andsubjecting said sintered product to the hydrophilicity-impartingtreatment for coating said substances.
 14. A process according to claim13, wherein the hydrophilicity-imparting treatment is the coating of thesilicon oxides.
 15. A process according to claim 13, wherein theskeleton has pores with an average pore size of 5 to 100 μm, the averagevoid size is 100 to 2,000 μm, and the porosity content of the wholeporous material is not more than 90% by volume and not less than 70% byvolume.